JPH10158513A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition remarkably reduced in burrs on molding and excellent in moldability and mechanical characteristics, while maintaining the physical properties (high rigidity and heat resistance) of a polyarylene sulfide resin. SOLUTION: This thermoplastic resin composition comprises (a) a polyarylene sulfide resin having a SH group content of >=10μmol/g, (b) a norbornene resin, (c) a filler in an amount of 0-400 pts.wt. per 100 pts.wt. of the total amount of the components (a) and (b), and, if necessary, (d) a linear functional group- containing copolymer consisting mainly of olefin units and unsaturated compound units having at least one kind of functional group selected from carboxyl group, acid anhydride group, oxazoline group and epoxy group in an amount of 0.1-30 pts.wt. per 100 pts.wt. of the total amount of the components (a) and (b).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition which has high rigidity and high heat resistance, remarkably reduces burrs generated during molding, and has excellent moldability and impact resistance.

[0002]

2. Description of the Related Art Polyarylene sulfide resin is a thermoplastic resin having excellent heat resistance, chemical resistance, electric properties, mechanical properties, dimensional stability, etc.
It is used as a sealing material for electronic components. However, since this resin is a highly crystalline polymer, it exhibits extremely high fluidity in a temperature range exceeding the melting point. For this reason, there is a problem that it is difficult to control the fluidity at the time of injection molding, burrs are generated on the molded product, and the yield of precision molded products is significantly reduced. Conventionally, attempts to improve the moldability by blending another thermoplastic resin with a polyarylene sulfide resin have been known (JP-B-53-13469, JP-A-2-180945, JP-A-2-180945, -28
No. 1564, JP-A-6-306287), it was not possible to suppress the occurrence of burrs during molding to such an extent that no practical problem was caused.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has been developed in the course of molding while maintaining physical properties such as high rigidity and high heat resistance of polyarylene sulfide resin. It is an object of the present invention to provide a thermoplastic resin composition which significantly reduces burrs and is excellent in moldability, mechanical properties and molded appearance.

[0004]

That is, the present invention provides:
(C) a filler (0) based on 100 parts by weight of the total amount of the polyarylene sulfide resin having an SH group content of 10 μmol / g or more and (b) the norbornene resin;
A thermoplastic resin composition containing 400 parts by weight. And a total amount of the components (a) and (b) of 10
(C) 0 to 400 parts by weight of a filler with respect to 0 parts by weight,
(D) a functional group-containing olefin copolymer having at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an oxazoline group and an epoxy group;
An object of the present invention is to provide a thermoplastic resin composition containing parts by weight.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. (A) The polyarylene sulfide resin has a main structural unit represented by a general formula: -Ar-S- (wherein, Ar represents a divalent aromatic, and S represents a sulfur atom). It is united. The divalent aromatic constituting the polyarylene group includes a p-phenylene group, an m-phenylene group,
6-naphthalene group, 4,4′-biphenylene group, p,
Representative examples include a p'-bibenzyl group and each of these substituents. Among these, poly-p-phenylene sulfide (PPS) having a non-substituted nucleus p-phenylene group is preferred from the viewpoint of moldability. In the present invention, (a) the polyarylene sulfide resin comprises:
It is preferable that the above structural unit is contained in an amount of 70 mol% or more in one molecule. If this constituent unit is less than 70 mol%, undesired results such as a decrease in the crystallinity of the obtained polyarylene sulfide resin, a low glass transition temperature, and poor physical properties of the molded product may be caused. Also,
In the present invention, (a) the polyarylene sulfide resin is an aromatic group having a bond of three or more valences, for example, 1,
A 2,4-bonded phenylene nucleus, an aliphatic group, a hetero atom-containing group and the like may be contained in less than 30 mol% in one molecule.

Further, as the (a) polyarylene sulfide resin, a straight-chain type resin alone or, depending on the purpose, a semi-cross-linked type and / or a cross-linked type may be used. It is also possible to use a mixture. When a semi-cross-linked type and / or a cross-linked type are used alone or in combination, the compatibility may be remarkably reduced and burrs may be generated during molding. Further, as the polyarylene sulfide resin (a), a modified polyarylene sulfide resin or a mixture of a modified polyarylene sulfide resin and a polyarylene sulfide resin can also be used. As the modified polyarylene sulfide resin, epoxy group, amino group, carboxyl group, acid anhydride group, oxazoline group, vinyl group,
Resins modified with functional groups such as acryloyl group, methacryloyl group, isocyanate group and mercapto group can be used. Of these, epoxy group-modified polyarylene sulfide resin and amino group-modified polyarylene sulfide resin are particularly preferable. These functional groups can be obtained by reacting with (b) an ester in the norbornene-based resin, or forming a block copolymer of the polyarylene sulfide resin and the norbornene-based resin by affinity with the ester, thereby increasing the compatibility between the two. In addition to improving the physical properties of the resin composition, it is possible to reduce the anisotropy of physical properties and molding workability, which are disadvantages of the polyarylene sulfide resin. The method for producing the polyarylene sulfide resin (a) includes a condensation reaction of a dihalogenated aromatic compound and a diol aromatic compound, a condensation reaction of a monohalogenated aromatic thiol, or a dihalogenated compound and an alkali sulfide or a hydrosulfide. A method utilizing a desalination condensation reaction of an alkali and an alkali or hydrogen sulfide and an alkali compound is exemplified, but the method is not limited thereto.

In the present invention, (a) the viscosity of the polyarylene sulfide resin is usually from 100 to 4,000 at a temperature of 300 ° C. and a strain rate of 1,000 sec ^-1 .
Poise. In the present invention, the SH group of the polyarylene sulfide resin (a) is preferable because the group at the polymer terminal of the resin has activity. (A) The SH content of the polyarylene sulfide resin is 10 μmol /
g or more, preferably 12 μmol / g or more, more preferably 15 to 70 μmol / g. When the content of the terminal SH group having activity is less than 10 μmol / g, the morphology of the obtained composition is deteriorated, and the molded appearance is deteriorated. Further, the amount of the (a) polyarylene sulfide resin used is preferably 20 to 99% by weight, more preferably 4 to 100% by weight, based on the total amount of the components (a) and (b).
It is from 0 to 95% by weight, particularly preferably from 50 to 90% by weight. Within this range, the heat resistance of the resin composition is good, and the occurrence of burrs is suppressed.

The (b) norbornene-based resin of the present invention is a polymer derived from a specific monomer represented by the following general formula (I), and specifically includes the following. Ring-opening polymer of specific monomer Ring-opening copolymer of specific monomer and copolymerizable monomer Hydrogenated polymer of the above ring-opening (co) polymer Free of the above ring-opening (co) polymer Hydrogenated copolymer after cyclization by Delkraft reaction Saturated copolymer of specific monomer and unsaturated double bond-containing compound

[0009]

Embedded image

[In the general formula (I), each of R ^{1 to} R ⁴ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or another monovalent organic group, each being the same or different. May be. R ¹ and R ² or R ³ and R ⁴ are
R ¹ or R ² and R ³ or R ⁴ may be combined with each other to form a monocyclic or polycyclic structure. m is 0 or a positive integer, and p is 0 or a positive integer. Among the specific monomers represented by the general formula (I), preferred are those in which R ¹ and R ³ are a hydrogen atom or a carbon atom having 1 carbon atom.
A hydrocarbon group of 10 to 10, wherein R ² and R ⁴ are a hydrogen atom or a monovalent organic group, and at least one of R ² and R ⁴ is a polar group having a polarity other than a hydrogen atom and a hydrocarbon group Wherein m is an integer of 0 to 3, p is an integer of 0 to 3, more preferably m + p = 0 to 4, further preferably 0 to 2, and particularly preferably 1. Among the specific monomers, the specific monomer whose polar group is a specific polar group represented by the formula — (CH ₂ ) _n COOR has a high glass transition temperature in which the hydrogenated product of the obtained ring-opening polymer is high. Is preferable because it has low hygroscopicity. In the above formula for the specific polar group, R is a hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group. In addition, n is usually from 0 to 5, but a smaller value of n is preferable because the glass transition temperature of the obtained ring-opened polymer becomes higher.
Is preferable in that the synthesis is easy and the obtained ring-opened polymer has a high glass transition temperature. Further, in the general formula 1, R ¹
Alternatively, R ³ is preferably an alkyl group, particularly a methyl group, and this alkyl group is particularly preferably a compound represented by the above formula — (CH ₂ ) _n C
It is preferable that the specific polar group represented by OOR is bonded to the same carbon atom as the bonded carbon atom. Further, the specific monomer in which m is 1 in the general formula 1 is preferable in that a ring-opened polymer having a high glass transition temperature can be obtained.

Specific examples of the specific monomer represented by the general formula (I) include bicyclo [2.2.1] hept-2-
Ene, tricyclo [5.2.1.02,6] -8-decene, tetracyclo [4.4.0.12,5. 17,10] -3
-Dodecene, pentacyclo [6.5.1.13,6. 02,
7． 09,13] -4-pentadecene, pentacyclo [7.
4.0.12,5. 19,12.08,13] -3-pentadecene, tricyclo [4.4.0.12,5] -3-undecene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethyl Bicyclo [2.2.1] hept-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept- 2-ene, 5-cyanobicyclo [2.2.1] hept-2-ene, 8-methoxycarbonyltetracyclo [4.4.0.12,5. 17
10] -3-dodecene, 8-ethoxycarbonyltetracyclo [4.4.0.12,5. 17,10] -3-dodecene,
8-n-propoxycarbonyltetracyclo [4.4.
0.12,5. 17,10] -3-dodecene, 8-isopropoxycarbonyltetracyclo [4.4.0.12,5. 1
7,10] -3-dodecene, 8-n-butoxycarbonyltetracyclo [4.4.0.12,5. 17,10] -3-dodecene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.12,5. 17, 10] -3-dodecene, 8
-Methyl-8-ethoxycarbonyltetracyclo [4.
4.0.12,5. 17,10] -3-dodecene, 8-methyl-8-n-propoxycarbonyltetracyclo [4.
4.0.12,5.17,10] -3-dodecene, 8-methyl-8-isopropoxycarbonyltetracyclo [4.
4.0.12,5.17,10] -3-dodecene, 8-methyl-8-n-butoxycarbonyltetracyclo [4.4.
0.12,5. 17,10] -3-dodecene,

Dimethanooctahydronaphthalene, ethyltetracyclododecene, 6-ethylidene-2-tetracyclododecene, trimethanooctahydronaphthalene, pentacyclo [8.4.0.12,5. 19, 12.08, 13]-
3-hexadecene, heptacyclo [8.7.0.13,6
. 110,17. 112,15. 02,7. 011,16] -4-eicosene, heptacyclo [8.8.0.14,7. 111,1
8． 113,16. 03,8. 012,17] -5-Heneicosene, 5-ethylidenebicyclo [2.2.1] hept-2
-Ene, 8-ethylidenetetracyclo [4.4.0.1
2,5. 17,10] -3-dodecene, 5-fluorobicyclo [2.2.1] hept-2-ene, 5-fluoromethylbicyclo [2.2.1] hept-2-ene, 5-trifluoromethylbicyclo [2.2.1] Hept-2-ene, 5-pentafluoroethylbicyclo [2.2.1]
Hept-2-ene, 5,5-difluorobicyclo [2.
2.1] Hept-2-ene, 5,6-difluorobicyclo [2.2.1] hept-2-ene, 5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2
-Ene, 5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5-methyl-5-trifluoromethylbicyclo [2.2.1] hept-2-
Ene, 5,5,6-trifluorobicyclo [2.2.
1] hept-2-ene, 5,5,6-tris (fluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrafluorobicyclo [2.2.
1] Hept-2-ene, 5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,5-difluoro-6,6-bis (trifluoro Methyl) bicyclo [2.2.1] hept-2-
Ene, 5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-5-trifluoromethylbicyclo [2.2.1] hept-2-ene, 5-fluoro-5-pentafluoroethyl-6,6-bis (trifluoromethyl) bicyclo [ 2.2.1] Hept-2-ene, 5,6-difluoro-5-heptafluoro-iso
-Propyl-6-trifluoromethylbicyclo [2.
2.1] Hept-2-ene, 5-chloro-5,6,6-
Trifluorobicyclo [2.2.1] hept-2-ene, 5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,
5,6-trifluoro-6-trifluoromethoxybicyclo [2.2.1] hept-2-ene, 5,5,6-trifluoro-6-heptafluoropropoxybicyclo [2.2.1] hept- 2-ene,

8-fluorotetracyclo [4.4.0.
12,5. 17,10] -3-dodecene, 8-fluoromethyltetracyclo [4.4.0.12,5. 17,10] -3-dodecene, 8-difluoromethyltetracyclo [4.4.
0.12,5. 17,10] -3-dodecene, 8-trifluoromethyltetracyclo [4.4.0.12,5. 17,10]
-3-dodecene, 8-pentafluoroethyltetracyclo [4.4.0.12,5. 17,10] -3-dodecene,
8,8-difluorotetracyclo [4.4.0.12,5
. 17,10] -3-dodecene, 8,9-difluorotetracyclo [4.4.0.12,5. 17,10] -3-dodecene, 8,8-bis (trifluoromethyl) tetracyclo [4.4.0.12,5. 17, 10] -3-dodecene, 8,
9-bis (trifluoromethyl) tetracyclo [4.
4.0.12,5. [17,10] -3-dodecene, 8-methyl-8-trifluoromethyltetracyclo [4.4.0.
12,5. 17,10] -3-dodecene, 8,8,9-trifluorotetracyclo [4.4.0.12,5. 17,10] −
3-dodecene, 8,8,9-tris (trifluoromethyl) tetracyclo [4.4.0.12,5.17,10] -3
-Dodecene, 8,8,9,9-tetrafluorotetracyclo [4.4.0.12,5. 17,10] -3-dodecene,
8,8,9,9-Tetrakis (trifluoromethyl) tetracyclo [4.4.0.12,5. 17,10] -3-dodecene, 8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.12,5. 17,1
0] -3-dodecene, 8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.
12,5. 17,10] -3-dodecene, 8,8,9-trifluoro-9-trifluoromethyltetracyclo [4.
4.0.12,5. [17,10] -3-dodecene, 8,8,9
-Trifluoro-9-trifluoromethoxytetracyclo [4.4.0.12,5. 17,10] -3-dodecene,
8,8,9-Trifluoro-9-pentafluoropropoxytetracyclo [4.4.0.12,5. 17,10] -3
-Dodecene, 8-fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.12,5. 17, 10] -3-dodecene, 8,
9-difluoro-8-heptafluoroiso-propyl-9-trifluoromethyltetracyclo [4.4.0.
12,5. 17, 10] -3-dodecene, 8-chloro-8,
9,9-trifluorotetracyclo [4.4.0.12,
Five . 17, 10] -3-dodecene, 8,9-dichloro-8,
9-bis (trifluoromethyl) tetracyclo [4.
4.0.12,5. 17, 10] -3-dodecene, 8- (2,
2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.12,5. 17, 10] -3-dodecene, 8
-Methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.12,5. 17,1
0] -3-dodecene and the like.

Among them, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^{7,1 0} ] -3-dodecene,
8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-dodecene, 8-ethyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, pentacyclo [7.4.0.1 ^2,5 . ^19,12 . ^0,13 ] -3-pentadecene, and from the viewpoint of compatibility with the component (a), 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . And most preferably 1 ^{7,1 0]} -3- dodecene. The above-mentioned specific monomers do not necessarily need to be used alone, and a ring-opening copolymerization reaction can be performed using two or more kinds. Also, polybutadiene, polyisoprene,
Ring opening of specific monomers in the presence of unsaturated hydrocarbon-based polymers containing a carbon-carbon double bond in the main chain such as styrene-butadiene copolymer, ethylene-non-conjugated diene copolymer, and polynorbornene It may be polymerized. The hydrogenated product of the ring-opening copolymer obtained in this case is useful as a raw material for a resin having high impact resistance.

<Copolymerizable Monomer> (b) The norbornene-based resin may be obtained by subjecting the above-mentioned specific monomer to ring-opening polymerization alone. A copolymer obtained by ring-opening copolymerization with a monomer may be used. Specific examples of the copolymerizable monomer used in this case include cyclobutene, cyclopentene, cycloheptene, cyclooctene, bicyclo [2.2.1] hept-2-ene, and tricyclo [5.2.1.0 ^{2, 6} ] -3
And cycloolefins such as 1-decene, 5-ethylidene-2-norbornene, and dicyclopentadiene. Furthermore, it is specified in the presence of unsaturated hydrocarbon polymers containing a carbon-carbon double bond in the main chain, such as polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-nonconjugated diene polymer, and polynorbornene. The monomer may be subjected to ring-opening polymerization. The hydrogenated ring-opening polymer obtained in this case is useful as a raw material for a norbornene-based resin having high impact resistance.

<Unsaturated Double Bond-Containing Compound> Further, in order to obtain a norbornene resin comprising a saturated copolymer,
Examples of the unsaturated double bond-containing compound used together with the specific monomer include ethylene, propylene, butene, and the like. The amount of the copolymerizable monomer used together with the specific compound of the formula (I) is preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 1 to 30% by weight based on the total amount of both. is there. Also,
The amount of the unsaturated double bond-containing compound to be used is preferably 30% by weight or less, more preferably 20% by weight, based on all monomers.
% By weight, especially from 1 to 10% by weight.

<Ring-opening polymerization catalyst> In the present invention, a ring-opening polymer of a specific monomer, a ring-opening copolymer of a specific monomer and a copolymerizable monomer, and a ring-opening (co) polymer After cyclization of the hydrogenated polymer and the ring-opening (co) polymer by the Friedel-Crafts reaction, the ring-opening polymerization reaction for obtaining the hydrogenated copolymer is carried out in the presence of a metathesis catalyst. This metathesis catalyst comprises (i) W, Mo and Re
And (ii) a group IA element (eg, Li, Na, K, etc.), a group IIA element (eg, Mg, Ca, etc.), a group IIB element (eg, Zn, Cd, Hg, etc.), Group IIIA elements (eg, B, Al, etc.), Group IVA elements (eg, Si,
Sn, Pb, etc.) or a group IVB element (eg, Ti,
Zr) is a catalyst comprising a combination with at least one selected from compounds having at least one of the element-carbon bond or the element-hydrogen bond. In this case, in order to enhance the activity of the catalyst, an additive described below (iii) may be added.
Representative examples of W, Mo, or Re compounds suitable as the component (i) include WCl ₆ , MoCl ₅ , and ReOCl.
₃ may include compounds described in the eighth tribute lower left column JP-A-1-132626 sixth row to paragraph 8, right upper column, line 17, such as. (Ii) As a specific example of the component, nC ₄ H ₉
Li, (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl, (C _{2
H 5) 1,5 AlCl 1,5, (} C 2 H 5) AlCl 2, methylalumoxane, the JP-A-1-132626 eighth Contribution right upper column, line 18 - paragraph 8, right lower column, such as LiH The compounds described in line 3 can be mentioned. An additive (iii)
Representative examples of components include alcohols, aldehydes,
Ketones, amines and the like can be preferably used, and compounds described in JP-A-1-132626, No. 8, right lower column, line 16 to item 9, upper left column, line 17 can be used. it can. The amount of the metathesis catalyst to be used is determined by the molar ratio of the component (i) to the specific monomer, which is “(i)
Component: specific monomer "is usually 1: 500 to 1:50,
000, preferably 1: 1,000 to 1: 1
The range is set to 0000. (I) component and (ii)
The ratio of the components is (i) :( ii) is 1:
It is in the range of 1-1: 50, preferably 1: 2-1: 30. The molar ratio of component (i) to component (iii) is such that (iii) :( i) is in the range of 0.005: 1 to 15: 1, preferably 0.05: 1 to 7: 1. .

In the present invention, the catalyst for synthesizing a saturated copolymer of a specific monomer and an unsaturated double bond-containing compound is at least one selected from a titanium compound, a zirconium compound and a vanadium compound. And an organoaluminum compound as a co-catalyst. Here, as the titanium compound, titanium tetrachloride,
Titanium trichloride and the like, and zirconium compounds such as bis (cyclopentadienyl) zirconium chloride,
Bis (cyclopentadienyl) zirconium dichloride and the like can be mentioned. Further, as the vanadium compound, a general formula VO (OR) _a X _b or V (OR) _c X _d [where R is a hydrocarbon group, X is a halogen atom, and 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ (a + b) ≦ 3, 0
≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ (c + d) ≦ 4. ]
Or an electron donating adduct thereof. Examples of the electron donor include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, oxygen-containing electron donors such as alkoxysilanes, ammonia, and amines. , Nitriles and nitrogen-containing electron donors such as isocyanates. further,
As the organoaluminum compound as the co-catalyst, at least one selected from compounds having at least one aluminum-carbon bond or aluminum-hydrogen bond is used. In the above, for example, when a vanadium compound is used, the ratio of the vanadium compound to the organoaluminum compound is such that the ratio of aluminum atoms to vanadium atoms (Al / V) is 2 or more, preferably 2 to 50, and particularly preferably 3 to 20. Range.

<Solvent for Polymerization Reaction> Examples of the solvent (solvent constituting the molecular weight modifier solution, solvent for the specific monomer and / or metathesis catalyst) used in the ring-opening polymerization reaction include, for example, pentene, hexane, heptane, octane ,
Nonane, alkanes such as decane, cyclohexane, cycloheptane, cyclooctane, decalin, cycloalkanes such as norbornane, benzene, toluene, xylene, ethylbenzene, aromatic hydrocarbons such as cumene, chlorobutane, bromohexene, methylene chloride, Compounds such as dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform and tetrachloroethylene, such as halogenated alkanes and aryl algenides;
Ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate, saturated carboxylic esters such as dimethoxyethane, dibutyl ether, tetrahydrofuran, ethers such as dimethoxyethane, and the like, and these alone or They can be used in combination. Of these, aromatic carbons are preferred. The amount of solvent used is "solvent: specific monomer (weight ratio)"
Is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1.

<Molecular weight regulator> The molecular weight of the norbornene-based polymer can be controlled by adjusting the polymerization temperature, the type of catalyst, and the type of solvent. In the present invention, the molecular weight regulator is made to coexist in the reaction system. Adjust by: Here, preferred molecular weight regulators include, for example, ethylene,
Propene, 1-butene, 1-pentene, 1-hexene,
Examples thereof include α-olefins such as 1-heptene, 1-octene, 1-nonene, and 1-decene, and styrene, of which 1-butene and 1-hexene are particularly preferable. These molecular weight regulators can be used alone or
A mixture of more than one species can be used. The amount of the molecular weight modifier used may be a specific monomer 1 which is used in the ring-opening polymerization reaction.
0.005 to 0.6 mol, preferably 0.1 to 0.5 mol per mol.
02 to 0.5 mol. The molecular weight of the norbornene-based polymer used in the present invention is 0.1 in intrinsic viscosity [η] _inh .
Those having a range of 2 to 5.0 are preferred.

<Hydrogenation catalyst> The ring-opened polymer obtained as described above can be hydrogenated using a hydrogenation catalyst. The hydrogenation reaction is carried out in a usual manner, that is, by adding a hydrogenation catalyst to a solution of the ring-opening polymer, and adding a normal pressure to the solution.
300 atm, preferably 3 to 200 atm of hydrogen gas
The reaction is carried out at a temperature of from 200 to 200C, preferably from 20 to 180C. As the hydrogenation catalyst, those used in ordinary hydrogenation reactions of olefinic compounds can be used. Examples of the hydrogenation catalyst include a heterogeneous catalyst and a homogeneous catalyst. As a heterogeneous catalyst, palladium, platinum, nickel, rhodium, ruthenium and other noble metal catalyst materials, carbon, silica,
Examples include a solid catalyst supported on a carrier such as alumina and titania. Examples of the heterogeneous catalyst include nickel / triethylaluminum naphthenate, nickel acetylacetonate / triethylaluminum, cobalt / actylate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, and chlorotris (triphenylphosphine) rhodium. , Dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium and the like. The form of the catalyst may be powder or granular. These hydrogenation catalysts are used at a ratio of a ring-opening polymer: hydrogenation catalyst (weight ratio) of 1: 1 × 10 ⁻⁶ to 1: 2. As described above, the hydrogenated polymer obtained by hydrogenation has excellent thermal stability, and its characteristics do not deteriorate even by heating during molding or use as a product. Here, the hydrogenation rate is usually 50% or more, preferably 70% or more, more preferably 90% or more, further preferably 95% or more, particularly 97% or more.
% Or more.

The amount of the (b) norbornene-based resin used is preferably 80 to the total amount of the components (a) and (b).
-1% by weight, preferably 60-5% by weight, more preferably 50-10% by weight. If it exceeds 80% by weight,
Heat resistance may be reduced, while if less than 1% by weight,
Burrs may be significantly generated.

The thermoplastic resin composition of the present invention may be further blended with a filler (c) to obtain a thermoplastic resin composition having more excellent heat resistance and dimensional accuracy of the obtained molded article. (C) Examples of the filler include a fibrous material having an aspect ratio (average length L / average system D) greatly exceeding 1, a bead having an aspect ratio of about 1 to 5, a powdery material, and a tetrapod shape. One having a three-dimensional structure is exemplified. Here, in order to increase the rigidity of the obtained resin composition, the fibrous filler preferably has an aspect ratio of 20 to 500, more preferably 30 to 300. If the aspect ratio exceeds 500, the rigidity increases, but the anisotropy increases, which is not practical. In order to improve the anisotropy, it is preferable that the aspect ratio is small.
0 or less, preferably 20 or less, more preferably 1-1.
0. Further, the average diameter of the fibrous filler is preferably 0.1 to 250 μm, and if it is less than 0.1 μm, the rigidity does not increase, while if it exceeds 250 μm, the mechanical properties,
The molded appearance may be deteriorated. On the other hand, the powdery filler has an average particle diameter of 100 μm or less, preferably about 60 μm or less. When a powdery filler is used, a molded article having a good appearance can be obtained.

Among them, the fibrous filler includes inorganic fibers such as glass fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber, metal fiber, and inorganic fibers such as potassium titanate whisker and zinc oxide whisker. Whiskers and carbon fibers. Some of the inorganic whiskers have a three-dimensional structure such as a tetrapod by the manufacturing method, but by using this, the rigidity is improved and the anisotropy during molding is improved. can do. Examples of the powdery filler include wollastonite, sericite, kaolin, mica, clay, pentonite, asbestos, talc, silicates such as arina silicate, alumina, silicon chloride, magnesium oxide, zirconium oxide, and oxide. Metal compounds such as titanium, calcium carbonate,
Examples include carbonates such as magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, boron nitride, silicon carbide, silica and the like, which may be hollow. These fillers can be used in combination of two or more, and can be used after being pretreated with a silane coupling agent as needed. Examples of the silane coupling agent include vinyl silane, acrylic silane, amino silane, epoxy silane,
Chlorosilane, mercaptosilane, peroxysilane and the like can be mentioned. (C) The use ratio of the filler is 0 to 400 with respect to 100 parts by weight of the total amount of the components (a) and (b).
It is 5 parts by weight, preferably 5 to 300 parts by weight, more preferably 20 to 150 parts by weight, and when it exceeds 400 parts by weight, moldability deteriorates.

(D) The functional group-containing olefin copolymer is
It is a copolymer having at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an oxazoline group and an epoxy group. This component (d) is disclosed in
Although a polymer having a multilayer structure (graft structure) as disclosed in JP-A-06287, paragraph 5, column 7, line 29 to column 5, column 8, line 44 can be used, block copolymers are preferred. It is a united or random copolymer. here,
(D) The functional group-containing copolymer is, for example, a binary, ternary or multi-component copolymer of an olefin and an unsaturated compound having the above functional group and, if necessary, another unsaturated compound. Can be manufactured.

(D) The olefin in the functional group-containing olefin copolymer is preferably ethylene or propylene, and particularly preferably ethylene. Examples of unsaturated compounds containing a carboxyl group include acrylic acid, methacrylic acid, and maleic acid. Examples of unsaturated compounds containing an anhydride group include maleic anhydride and itaconic anhydride. Examples of unsaturated compounds containing an oxazoline group include vinyl oxazoline. Examples of the epoxy group-containing unsaturated compound include glycidyl methacrylate and allyl glycidyl ether. Among these, preferred functional groups are an epoxy group,
It is an acid anhydride group. (D) The amount of olefin in the functional group-containing olefin copolymer is usually 40 to 99.5% by weight,
Preferably 50 to 99% by weight, the amount of the functional group-containing unsaturated compound is usually 50 to 0.5% by weight, preferably 40 to 1% by weight.
The amount of other unsaturated compounds is usually 0 to 50% by weight, preferably 0 to 30% by weight. As a method for producing the component (d), any of the well-known methods such as a chain transfer method and an ionizing radiation irradiation method may be used, but the most preferable method is described in JP-A-64-42256.
No. 9, ninth lower left column, first line to tenth upper left column, ninth line. Component (d) is used in an amount of 0.1 to 30 with respect to 100 parts by weight of the total of components (a) and (b).
Parts by weight, preferably 1 to 20 parts by weight, particularly preferably 3 parts by weight.
１５15 parts by weight. If the amount is less than 0.1 part by weight, the mechanical properties and the appearance of the molded product are reduced, and the area of the burrs is also increased.

If necessary, other thermoplastic resins or elastomers can be added to the resin composition of the present invention in an amount of about 50 parts by weight or less based on 100 parts by weight of the resin composition of the present invention. As the other thermoplastic resin or elastomer, specifically, a styrene resin, a vinyl chloride resin, an acrylic resin, a polyphenylene ether resin,
Polycarbonate resin, polyester resin, polyamide resin, polyether sulfone resin, polysulfone resin,
Polyimide resin, polyetherimide resin, styrene
Examples thereof include a hydrogenated product of a butadiene (block, random) copolymer, a hydrogenated product of an acrylonitrile-butadiene copolymer, an acrylic rubber, and an ethylene-propylene rubber.

The resin composition of the present invention may optionally contain a flame retardant. Examples of the flame retardant include halogen-based flame retardants, non-halogen-based flame retardants, metal oxides and inorganic flame retardants. Among them, examples of the halogen-based flame retardant include ammonium bromide, tetrabromobisphenol A, tetrabromophthalic anhydride, hexabromobenzene, hexabromocyclododecane, bis (bromoethyl ether) tetrabromobisphenol A, brominated polycarbonate, brominated polycarbonate, Brominated flame retardants such as polystyrene, chlorinated paraffin, chlorinated polyethylene, chlorinated flame retardants such as organochlorinated flame retardants (hetic acid, dechlorane plus, phthalic anhydride tetrachloride), tris (chloropropyl) phosphate, Halogen-containing phosphoric acid esters such as tris (2,3-dibromopropyl) phosphate are exemplified. These halogen-based flame retardants include Sb ₂
The combined use of O ₃ increases the flame retardant effect. Examples of the non-halogen flame retardant include triphenyl phosphate, cresyl diphenyl phosphate, and aromatic diphosphate represented by the following general formula (II).

[0029]

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[In the formula (II), R ⁵ or R ⁶ is the same or different and is a lower alkyl group, R ⁷ and R ⁸ are the same or different and is a hydrogen atom or a lower alkyl group, and Y is -CH _{2- , -C (CH 3) 2 -} , - S -, - SO 2 -, -
O-, -CO-, -N = N- groups, k is 0 or 1, n
Represents an integer of 0 to 4. ], Melamine, cyanuric acid, melamine cyanurate, tris-
(3,5-di-t-butyl-4-hydroxybenzyl)
Triazines such as isocyanurate, guanidines such as 1,3-diphenylguanidine, 1,3-diethyltriguanidine, thiazoles such as 2-mercaptobenzothiazole, 2,2′-dithiobisbenzothiazole, dimethyl Dithioacid salts such as zinc dithiocarboxylate, zinc diethyldithiocarboxylate, zinc N-ethyl-N-phenyldithiocarboxylate, 2- [2-hydroxy-3- (3,4,5,6-tetra-hydrophthalimide- Benzotriazoles such as methyl) -5-methylphenyl] benzotriazole and 2- (2-hydroxy-3,5-tert-butylphenyl) benothriazole, and nitrogen-based flame retardants such as derivatives or salts thereof. Is mentioned.

The above-mentioned phosphorus-based flame retardant preferably has a melting point of 100 ° C. or more, particularly preferably 160 ° C. or more. If the melting point of the phosphorus-based flame retardant is less than 100 ° C., the impact resistance and heat resistance of the resulting composition may be significantly reduced, which is not preferable. Further, the nitrogen-based flame retardant preferably has a melting point of 140 ° C. or higher, particularly preferably 160 ° C. or higher, and / or has a sublimation point of preferably 200 ° C.
° C or higher, particularly preferably 280 ° C or higher. If the melting point of the nitrogen-based flame retardant is lower than 140 ° C., the impact resistance, heat resistance, and flame retardancy of the obtained composition may be reduced and / or if the sublimation point is lower than 200 ° C., the flame retardancy is remarkably low. May decrease. The non-halogen flame retardant may be a phosphoric acid amide compound bonded to a phosphoric acid group.

Other metal oxides and inorganic flame retardants include, for example, silicone compounds represented by polyorganosiloxanes such as dimethyl silicone gum and methyl hydrogen polysiloxane; guanidine derivatives such as guanidine phosphate; boric acid; Examples include zinc borate, novolak resins, antimony oxide, sodium antimonate, magnesium hydroxide, and aluminum hydroxide.
These flame retardants can be used alone or in combination of two or more. The proportion of the flame retardant used is (a) to (b)
Preferably from 0.1 to 100 parts by weight of the total amount of the components
100 parts by weight, more preferably 1 to 50 parts by weight, particularly preferably 2 to 40 parts by weight, if less than 0.1 part by weight may not be able to improve the flame retardancy, while 100 parts by weight If it exceeds, heat resistance and rigidity may decrease.

Further, an antioxidant such as 2,6-di-tert-butyl-4-methylphenol, 2- (1-methylcyclohexyl) -4,6- is added to the resin composition of the present invention.
Dimethylphenol, 2,2-methylene-bis (4-methyl-6-t-butylphenol), tris (di-nonylphenyl phosphite); an ultraviolet absorber such as p-
Butylphenyl salicylate, 2,2′-dihydroxy-4-methoxy-benzophenone, 2- (2′-dihydroxy-4′-m-octoxyphenyl) benzotriazole, “TINUVIN320” (manufactured by Ciba-Geigy), “TINUVIN329” ( A lubricant such as paraffin wax, stearic acid, hydrogenated oil, stearamide, methylene bis stearamide, m-butyl stearate, ketone wax,
Octyl alcohol, hydroxystearic acid triglyceride and the like may be added in necessary amounts.

Further, a nucleating agent may be added to the resin composition of the present invention. As the crystal nucleating agent, an inorganic substance,
Any organic substance can be used. Inorganic substances include simple substances such as zinc powder, aluminum powder, graphite, and carbon black; metal oxides such as zinc oxide, magnesium oxide, alumina, titanium dioxide, manganese dioxide, silicon dioxide, and iron tetroxide; and boron nitride. Inorganic salts such as nitrides, sodium carbonate, calcium carbonate, magnesium carbonate, calcium sulfate, calcium silicate, barium sulfate, calcium phosphate,
Clays such as talc, kaolin, clay, and clay can be used. In addition, as organic substances, organic salts such as calcium oxalate, sodium oxalate, calcium benzoate, calcium phthalate, calcium tartrate, and magnesium stearate, heat-resistant polymers, and crosslinked products of heat-resistant polymers are used. be able to. Of these nucleating agents, preferably boron nitride; talc,
Clays such as kaolin, clay and clay; heat-resistant polymers having a crosslinked or branched structure;

Some of the above crystal nucleating agents overlap those of the filler (c), but these substances can fulfill both functions. The amount of the crystal nucleating agent used is preferably 0.002 to 5 parts by weight, more preferably 0.02 parts by weight, per 100 parts by weight of the polyarylene sulfide resin (a).
If the amount is less than 0.002 parts by weight, the effect of increasing the crystallization rate may not be sufficient. On the other hand, if it exceeds 5 parts by weight, heat resistance and flexural modulus may be undesirably reduced. Since the nucleating agent can control the crystallization rate of the polyarylene sulfide resin (a), the crystallization is terminated when the resin composition enters the mold by injection molding, thereby reducing the formation of burrs. can do. Further, since the crystal nucleating agent is a low molecular compound, it also has an effect as a plasticizer, and can improve the fluidity and moldability of the resin composition of the present invention in a molten state.

Further, a sliding agent may be added to the resin composition of the present invention for the purpose of improving slidability. As the sliding agent, both inorganic and organic substances can be used. As inorganic sliding agents, inorganic fibers such as glass fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber, metal fiber, carbon fiber,
Inorganic whiskers such as potassium titanate whiskers, silicone carbide whiskers, carbon graphite whiskers, silicon nitride whiskers, α-alumina whiskers, zinc oxide whiskers, particulate glass, ceramics, carbon and scaly mica, glass, etc. Chromium such as inorganic powder and molybdenum disulfide,
Molybdenum, tungsten (a VIA group metal) sulfide, and the like can be given. Examples of the organic sliding agent include polyamide fibers, wholly aromatic polyamide fibers (aramid fibers), organic fibers such as polyester fibers and cellulose fibers, polytetrafluoroethylene, and tetrafluoroethylene / perfluoroalkylvinyl ether copolymer. , Fluorocarbon polymers such as tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, polychlorotrifluoroethylene, chlorotrifluoroethylene / ethylene copolymer, polyvinylidene fluoride and polyvinyl fluoride , Ultra high molecular weight polyethylene particles, polyarylene thioether ketone particles, aromatic polyester particles and other polymer powders, silicone oil, aromatic oil, fluorine oil, hardened oil, polyethylene wax, ethylene Including lubricants such as down-bis-stearamide and the like. In addition,
Some of the above-mentioned sliding agents overlap the filler (c), but these substances can fulfill both functions. The above-mentioned sliding agents can be used alone or in combination of two or more. The use ratio of the sliding agent is preferably 0.01 to 4 with respect to 100 parts by weight of the total amount of the components (a) and (b).
00 parts by weight, more preferably 5 to 300 parts by weight. If the amount is less than 0.01 part by weight, the desired slidability may not be obtained.
Impact resistance may decrease.

The resin composition of the present invention comprises a single-screw extruder,
Using a mixer such as a multi-screw extruder, a Banbury mixer, a kneader, and a mixing roll, the components (a) to (c) and, if necessary, further (d) a specific functional group-containing copolymer and other additives are added. Obtained by mixing.
As an example of the method for producing the resin composition of the present invention, after mixing each component with a mixer, using an extruder, 240 to 3
A method of obtaining a granulated product by melt-kneading at 60 ° C., and a more convenient method include a method of directly mixing and kneading each component in a molding machine to obtain pellets. In addition, there is a method in which a resin component is kneaded using a twin-screw extruder, and then a filler is added later to form a pellet. The resin composition of the present invention thus obtained is particularly excellent in heat resistance and has a deflection temperature under load of 100 to 280 ° C. or higher, preferably 12 to 280 ° C.
0 to 280 ° C or higher. When the deflection temperature under load is less than 100 ° C., heat resistance and high-temperature rigidity are low. In order to adjust the deflection temperature under load of the resin composition of the present invention, the ratio of (a) a polyarylene sulfide resin having an active SH group content of 10 μmol / g or more to (b) a norbornene resin is changed. Alternatively, the amount of the compatibilizing agent (d) or other thermoplastic resin or elastomer may be varied.

The resin composition of the present invention is formed into a molded product by applying various known molding methods such as injection molding, compression molding, extrusion molding, and blow molding. . The resin composition of the present invention is used as an automotive component, for example, a cylinder head cover, an underhood component, a clean fan, a radiator tank, a relay cap, a window screen, and the like, as an electronic component.
For example, light emitting diodes (visible light diodes, infrared light emitting diodes, optical communication light emitting diodes), transistors, integrated circuits, phototransistors, EPROMs, photocouplers, photointerrupters, packages such as CCDs, capacitors, LC filter cases, tact SWs, slides For OA supply parts such as SW, for example, heat shield of copier, printer parts, motor parts, etc.
As electric and home appliance parts, for example, FDD carriage / bearing, optical disk optical pickup base, VTR / cylinder base, rotary connector, motor brush holder / commutator, electromagnetic cooker coil base,
For microwave oven parts (stirrer shaft, tray, turntable ring), dryer nozzle, steam iron valve, condenser lens case for optical fiber, etc., as mechanical parts, for example, watch board, chemical pump case
It can be used for various applications such as impellers, gear pumps, rheometers, general-purpose engine carburetors and heat insulators.

A preferred embodiment of the present invention is as follows. (A) When the polyarylene sulfide resin is poly-P-
A thermoplastic resin composition which is phenylene sulfide. (B) The specific monomer constituting the norbornene resin is 8
-Methyl-8-methoxycarbonyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene. (D) A thermoplastic resin composition wherein the functional group-containing copolymer is an ethylene-epoxy group-containing unsaturated compound and an acid anhydride group-containing unsaturated compound copolymer, more preferably an ethylene-glycidyl methacrylate copolymer.

[0040]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples. In the examples, parts and% are by weight unless otherwise specified. Various measurements in the examples are as follows. Active end group content 15 g of polyarylene sulfide resin obtained by polymerization
To 100 g of a water / N-methylpyrrolidone (= 1/1) solution
Under a pressure of 100 atm. After filtering the insoluble components, the concentration of the solution after filtration is determined. The obtained filtrate is titrated with a 0.01 N aqueous solution of sodium hydroxide to determine the content of active terminal group (μmol / g) per 1 g of the polymer. Glass transition temperature differential scanning calorimeter (SSC-, manufactured by Seiko Instruments Inc.)
580) in a nitrogen atmosphere in a nitrogen atmosphere at a temperature rising rate of 20
It was measured at ° C / min. Hydrogenation rate In the case of hydrogenated homopolymer, 60 MHz, ¹ H-N
It was measured by MR. Heat resistance (deflection temperature under load) Measured at a load of 10 kgf and a heating rate of 50 ° C./hour according to JIS K6719 using a test piece having a thickness of ”″. Formability (MFR) According to JIS K7210 The melt flow rate (MFR) was measured under the conditions of 316 ° C. × 5 kgf, and the unit is g / 10 minutes.

Burr length Center mold disk mold (outer peripheral gap 10 μm)
m, molded product size φ130 × t1.2 mm), and in order to match the molding conditions between materials having different fluidities, the minimum filling pressure for each material was determined by trial and error.
The burr length at the outer peripheral portion when a cm ² pressure was applied was measured. The molding temperature was 315 ° C. and the mold temperature was 10
0 ° C. When the length of the burr is 0.35 mm or less, it is at a level where there is no practical problem.
5 mm or less. Using a bending strength and a bending modulus test piece (1/8 "× 1/2" × 5/2 "),
Flexural strength (FS) and flexural modulus (FMo) were measured according to STM D790. Molding conditions; Injection molding machine = Allrounder Hydronica D manufactured by ARBURG Cylinder temperature = 315 ° C Mold temperature = 150 ° C Holding time = 5 seconds Cooling time = 8 to 22 seconds Cushion amount = 3 to 5 mm Cycle time = about 19 ３３33 seconds Injection pressure = depends on sample. Molded appearance The above test piece was visually observed and judged according to the following criteria. ○: no problem △: × pearly is observed in the vicinity of the gate: than the average dispersed particle diameter above test piece pearly is observed throughout the molded article cut thick sections 0.1-10 several [mu] m, transmission electron Observation and photography were performed with a microscope (TEM), and the obtained TEM photograph was taken into an image analyzer to determine the average particle size of the dispersed phase.

Reference Example Each component was adjusted when producing a resin composition. (A) Component Linear polyphenylene sulfide (PPS): manufactured by Topren Co., Ltd. (a-1); LN-1G, active terminal group content 25 μm
ol / g (a-2); LN-2G, active terminal group content 32 μm
ol / g Semi-crosslinked PPS: manufactured by Topren Co., Ltd. (a-3); T-1, active terminal group content 16.5 μm
ol / g (a-4); T-2, active terminal group content 18.6 μm
ol / g (a-5); T-3, active terminal group content 8.4 μm
ol / g (a-6); T-4, active terminal group content 6.5 μm
ol / g

(B) Component (b-1) Norbornene-based resin I As a specific monomer, 8-methyl-8-methoxycarbonyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 250 parts of 1-hexene as a molecular weight regulator, and 500 parts of toluene
Were charged into a reaction vessel purged with nitrogen, and heated to 80 ° C. 0.58 parts of a toluene solution of triethylaluminum (1.5 mol / L) as a polymerization catalyst and t-
Denaturation of WCl ₆ with butanol and methanol, t-
WCl ₆ solution with a molar ratio of butanol to methanol and tungsten of 0.35: 0.3: 1 (concentration of 0,1).
(05 mol / L) and heated and stirred at 80 ° C. for 3 hours to obtain a polymer solution. The polymerization addition rate in this polymerization reaction was 97%.

[0044]

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4,000 parts of the obtained polymer solution was put into an autoclave, and RuHCl (CO) [P (C ₆
H _{5) 3] 3} 0.48 parts was added, 100k hydrogen gas pressure
g / cm ² and a reaction temperature of 165 ° C. for 3 hours.
The mixture was stirred to perform a hydrogenation reaction. After cooling the obtained reaction solution, hydrogen gas was released to obtain a hydrogenated polymer solution. The polymer solution was coagulated with a large amount of methanol and dried to isolate the polymer. The glass transition temperature (Tg) of this polymer is 170 ° C., and the hydrogenation rate is substantially 100%.
And gel permeation chromatography (G
The weight average molecular weight (Mw) in terms of polystyrene measured by PC) was 55,000.

(B-2) Norbornene-based resin II As a specific monomer, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
-3-Dodecene (300 parts) in cyclohexane (2,000)
And 10 parts of 1-hexene was added as a molecular weight regulator, and the internal temperature was maintained at 30 ° C. To this solution, 100 parts of a 15% solution of triethylaluminum in cyclohexane,
50 parts of triethylamine and 20% of titanium tetrachloride
100 parts of a cyclohexane solution was added, and a ring-opening polymerization reaction was performed for 2 hours. The polymerization addition rate of this reaction was 95%.

[0047]

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To 500 parts of the cyclohexane solution of the obtained ring-opened polymer was added 1 part of palladium-carbon, and the mixture was charged into an autoclave, and hydrogen pressure was 70 kg / cm ² , 1 part.
The hydrogenation reaction was performed at 40 ° C. for 3 hours. After cooling the obtained reaction solution, hydrogen gas was released to obtain a hydrogenated polymer solution. The polymer solution was coagulated in a large amount of methanol and dried to isolate the polymer. The glass transition temperature (Tg) of this resin is 142 ° C., and the hydrogenation rate is 9
It was 9.9% or more, and the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) was 59,500.

(B-3) Norbornene Resin III A reaction vessel equipped with a stirring blade, a gas inlet tube, a thermometer and a dropping funnel was sufficiently replaced with nitrogen gas, and the inside of the reaction vessel was dehydrated and dried by molecular sheep. Toluene 2,
500 ML was charged. Under a nitrogen stream, pentacyclo [6.5.1.1] represented by the following structural formula (5) was placed in the flask.
^3,6 . 0 ^2,7 . [ ^09,13 ] -4-pentadecene, 25 mmol of ethylaluminum sesquichloride, and 2.5 mmol of dichloroethoxyoxovanadium in a dropping funnel. Through a gas introduction pipe, dry mixed gas of 200 L / hr of ethylene and 400 L / hr of nitrogen,
Passed through a flask maintained at 10 ° C. for 10 minutes.

[0050]

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From the dropping funnel, dichloroethoxyoxovanadium was added dropwise to start the copolymer reaction, and the copolymerization reaction was carried out at 10 ° C. while passing the above mixed gas.
After a lapse of 30 minutes, 30 ml of methanol was added to the reaction solution to stop the polymerization reaction. Subsequently, the polymer solution was coagulated in a large amount of methanol and dried to isolate a norbornene-based saturated copolymer. The glass transition temperature (Tg) of this polymer is 135 ° C., and the intrinsic viscosity [η] _inh measured in decalin at 130 ° C. is 0.62 dl /.
g.

(C) Component glass fiber; aspect ratio = 230, manufactured by Asahi Fiberglass Co., Ltd., 03MAFT523 (d) Component manufactured by Nippon Petrochemical Co., Ltd., Lexpearl RA3150 (ethylene-glycidyl methacrylate copolymer)

Examples 1 to 13 and Comparative Examples 1 to 7 Pellets were melt-kneaded at 310 ° C. using a twin screw extruder at 40 ° C. according to the formulation shown in Tables 1 to 3. Using the obtained pellets, injection molding was performed under the above injection conditions to obtain test pieces for evaluation. The evaluation results are shown in Tables 1 to 3.

[0054]

[Table 1]

[0055]

[Table 2]

[0056]

[Table 3]

According to Tables 1 and 2, the resin composition of the present invention can be mixed with a specific PPS with a norbornene-based resin to reduce the occurrence of burrs, which is a problem in PPS, to a level at which there is no practical problem. It can be seen that it is suppressed and has excellent mechanical properties and molded appearance. In particular, in systems where the amount of the norbornene-based resin used is 30% or more of the components (a) and (b), burr-free is achieved. On the other hand, as is apparent from Table 3, Comparative Examples 1 to 4 are examples in which the content of the terminal SH group having the activity of the component (a) is lower than the scope of the claims, and remarkable generation of burrs. A remarkable decrease in the mechanical properties and a remarkable deterioration in the molded appearance are observed. Furthermore, as seen in Comparative Examples 5 and 6, even in the system to which the component (d) as a compatibilizer was added, the molded appearance and mechanical properties were inferior. Comparative Example 7 is an example in which the use amount of the component (c) exceeds the upper limit, and molding workability is poor.

[0058]

The thermoplastic resin composition of the present invention comprises a specific polyarylene sulfide resin and a norbornene resin as essential components, and optionally a filler or / and a specific functional group-containing copolymer. Since it is a blended composition, it has high rigidity and excellent heat resistance, significantly reduces burrs generated during molding, and is excellent in moldability and mechanical properties.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 23:00)

Claims (2)

[Claims] (1) The SH group content is 10 μmol / g.
The above polyarylene sulfide resin and (b)
For a total amount of 100 parts by weight of the norbornene resin,
(C) A thermoplastic resin composition comprising 0 to 400 parts by weight of a filler. 2. A filler (c) from 0 to 40 based on 100 parts by weight of the total of the components (a) and (b) according to claim 1.
0 parts by weight and (d) a carboxyl group, an acid anhydride group,
A thermoplastic resin composition comprising 0.1 to 30 parts by weight of a functional group-containing olefin copolymer having at least one functional group selected from the group consisting of an oxazoline group and an epoxy group.